CN115179609A - Light dredging heat-insulation-preventing composite material and preparation method thereof - Google Patents
Light dredging heat-insulation-preventing composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a light dredging heat-insulation-preventing composite material, which comprises a reinforcement and an ablation-resistant matrix, wherein the reinforcement comprises a high-temperature-resistant inorganic fiber fabric layer and a high-heat-conductivity carbon fiber fabric layer, and each high-heat-conductivity carbon fiber fabric layer is sandwiched between two high-temperature-resistant inorganic fiber fabric layers; the ablation-resistant matrix comprises an ablation-resistant resin and inorganic particles. The invention also discloses a preparation method of the composite material, which comprises the steps of firstly laminating and needling the high-temperature-resistant inorganic fibers layer by layer to form an inorganic fiber fabric layer, then clamping the carbon fiber fabric between the two inorganic fiber fabric layers to obtain a sandwich structure reinforcement, and finally adopting solution gel and vacuum impregnation resin transfer molding method to prepare the composite material. The composite material has low density and thermal conductivity, extremely low linear ablation rate in a long-term aerobic-pneumatic-thermal environment, good thermal insulation and mechanical properties, and can be used for a large-area thermal insulation prevention structure of a space vehicle, and a thermal insulation prevention structure with high requirements on thermal insulation and bearing and urgent weight reduction requirements.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a light dredging heat-insulation-preventing composite material and a preparation method thereof.
Background
The aerospace craft generates serious pneumatic heating when reentering the atmosphere, the thermal protection system is one of the key subsystems which must be relied on for ensuring the normal work of electronic components and manned space in the aerospace craft, and the heat-proof material is a vital part in the thermal protection system, and the effectiveness of the heat-proof material is concerned with the success or failure of flight and even the life safety of human beings. With the gradual development of serial projects such as manned aerospace, lunar exploration project, future deep space exploration and manned lunar landing, the reentry speed of the aerospace craft is higher and higher, the faced thermal environment is more severe, higher requirements are also put forward on thermal protection materials, and the requirements on simplification and lightening of the thermal protection system structure and multi-functionalization are required, namely the heat protection and heat insulation functions are realized.
The carbon/phenolic aldehyde composite material and the quartz/phenolic aldehyde composite material are typical resin-based ablation heat-proof materials, and the density is 1.4-1.7 g/cm 3 The method is mainly applied to the high enthalpy and high heat flow pneumatic environment facing the traditional reentry aircraft. The heat resistance of the reinforced fiber determines the applicable environment of the ablation composite material to a great extent, quartz/phenolic aldehyde is suitable for medium-short time medium-low heat flow environment, and carbon/phenolic aldehyde is suitable for short-time high heat flow environment. Carbon fiber has low density, high temperature resistance and heat conductivityThe rate is high, the quartz fiber is easy to oxidize, the thermal conductivity is low, but the melting point is low, and when the ablation surface temperature exceeds 1600 ℃, the serious ablation retreating phenomenon occurs. The novel aerospace craft faces a long-term aerobic low-heat flow pneumatic environment, the surface temperature exceeds 1600 ℃, and the traditional compact ablation material has the defects of poor heat insulation performance, poor oxidation resistance, large ablation retreating amount, overweight and the like in the environment and can not meet the thermal protection requirement. The low density ablative materials used in the reentry module have excellent thermal insulation properties such as SLA-561, AVCOAT and H96, which maintain structural integrity by reinforcing the honeycomb, however, the ablation volume recedes more in an aerobic environment, and the long ablation causes aerodynamic profile changes, which affect the accuracy of aircraft reentry control.
Researches find that the lightweight phenolic impregnated ablation type heat-proof composite material takes porous phenolic resin as a matrix and has lower heat conductivity. The phenolic resin matrix can provide a certain heat insulation effect while ablation heat insulation is carried out, and the requirement of heat prevention/insulation is met. However, the porous organic resin matrix has a larger specific surface area than that of a common dense phenolic resin matrix, so that the generated porous carbonized layer has lower strength and a fragile structure, and is easy to oxidize in an aerobic environment to damage the structure of the porous carbon layer, thereby causing insufficient oxidation resistance and scouring resistance of the composite material.
Disclosure of Invention
The invention aims to overcome the defects and provides a light dredging heat-insulation-preventing composite material and a preparation method thereof. The composite material comprises a reinforcement body and an ablation-resistant matrix, wherein the reinforcement body is of a sandwich structure, the reinforcement body comprises a high-temperature-resistant inorganic fiber fabric layer and a high-heat-conductivity carbon fiber fabric layer, and each high-heat-conductivity carbon fiber fabric layer is sandwiched between two high-temperature-resistant inorganic fiber fabric layers; the ablation-resistant matrix comprises an ablation-resistant resin and inorganic particles. According to the preparation method of the composite material, firstly, high-temperature-resistant inorganic fibers are laminated layer by layer and needled to form a high-temperature inorganic fiber fabric layer, then the high-heat-conductivity carbon fiber fabric is clamped between the two high-temperature inorganic fiber fabric layers to obtain a sandwich structure reinforcement, and finally, the solution gel and vacuum impregnation resin transfer molding method is adopted to form the integral composite material. The composite material has low density and thermal conductivity, extremely low linear ablation rate in a long-term aerobic-pneumatic-thermal environment, good thermal insulation and mechanical properties, and can be used as a large-area thermal insulation prevention functional material for a space vehicle and a thermal insulation prevention structural material with high requirements on heat prevention and bearing and urgent weight reduction requirements.
In order to achieve the above purpose, the invention provides the following technical scheme:
a light dredging heat-proof composite material comprises a reinforcement body and an ablation-resistant matrix;
the reinforcement is of a sandwich structure and comprises a high-temperature-resistant inorganic fiber fabric layer and a high-heat-conductivity carbon fiber fabric layer, wherein each high-heat-conductivity carbon fiber fabric layer is sandwiched between two high-temperature-resistant inorganic fiber fabric layers;
the ablation-resistant matrix comprises an ablation-resistant resin and inorganic particles;
the total mass of the light dredging heat-insulation-preventing composite material is 100%, and the mass percentage of each component is as follows:
40-50% of high-temperature resistant inorganic fiber fabric;
10-20% of high-thermal-conductivity carbon fiber fabric;
30-50% of ablation-resistant resin;
1 to 5 percent of inorganic particles;
the high-temperature resistant inorganic fiber in the high-temperature resistant inorganic fiber fabric layer is one or the combination of more than one of quartz fiber, high silica fiber or alumina fiber; and the high-heat-conductivity carbon fibers in the high-heat-conductivity carbon fiber fabric layer are mesophase pitch carbon fibers.
Furthermore, the reinforcement comprises 1-3 high heat-conducting carbon fiber fabric layers.
Further, the high-temperature resistant inorganic fiber fabric layer is a needled felt of high-temperature resistant inorganic fibers;
the ablation-resistant substrate is a porous material with micron-sized pores;
the high-thermal-conductivity carbon fiber fabric layer is a unidirectional fabric, a two-dimensional multidirectional fabric or a three-dimensional multidirectional fabric;
the ablation-resistant resin is one or more of linear phenolic resin, high-carbon phenolic resin or organic silicon resin;
the inorganic particles are one or the combination of more than one of molybdenum silicide, silicon carbide or zirconium boride.
Furthermore, the density of the high-temperature resistant inorganic fiber fabric layer in the reinforcement body is 0.10-0.30 g/cm 3 The thickness is 1-20 mm.
Furthermore, the surface density of the high-thermal-conductivity carbon fiber fabric layer in the reinforcement body is 50-1000 g/m 2 The thickness is 0.5-10 mm, wherein the thickness refers to the total thickness of the high-heat-conduction carbon fiber fabric layer, and the high-heat-conduction carbon fiber fabric layer is obtained by layering more than or equal to 1 carbon fiber single-layer fabric;
the average density of the light dredging heat-proof composite material is 0.3-0.8 g/cm 3 。
Further, the thermal conductivity of the high thermal conductive carbon fibers in the high thermal conductive carbon fiber fabric layer is not lower than 500W/(m.K).
The preparation method of the light dredging heat-proof and heat-insulating composite material comprises the following steps:
carding the high-temperature-resistant inorganic fibers into a net tire, and needling a plurality of layers of net tires layer by layer in a laminated manner to form a high-temperature-resistant inorganic fiber fabric layer; the high-temperature resistant inorganic fiber is one or the combination of more than one of quartz fiber, high silica fiber or alumina fiber;
weaving continuous high-thermal-conductivity carbon fibers into a high-thermal-conductivity carbon fiber fabric to obtain a high-thermal-conductivity carbon fiber fabric layer; the high-thermal-conductivity carbon fibers are mesophase pitch carbon fibers;
laying a high-thermal-conductivity carbon fiber fabric layer on the surface of the high-temperature inorganic fiber fabric layer to obtain a high-porosity reinforcement with a sandwich structure;
mixing inorganic particles, a solvent and a dispersing agent, and performing ultrasonic dispersion to obtain inorganic particle slurry;
preparing ablation-resistant resin solution from ablation-resistant resin, a catalyst and a solvent, adding inorganic particle slurry into the ablation-resistant resin solution, and stirring to obtain an ablation-resistant matrix;
placing the reinforcement in a mold, introducing the ablation-resistant matrix into the mold by adopting a vacuum resin transfer process, and sequentially performing heating, heat preservation, demolding and drying to obtain the material with the density of 0.3-0.8 g/cm 3 The light dredging heat-proof and heat-insulating composite material.
Further, in the preparation method of the light dredging heat-proof and heat-insulating composite material, the ablation-resistant resin is one or more of linear phenolic resin, high-carbon phenolic resin or organic silicon resin;
the inorganic particles are one or the combination of more than one of molybdenum silicide, silicon carbide or zirconium boride.
Further, in the preparation method of the light dredging heat-proof insulation composite material, when the inorganic particles, the solvent and the dispersant are mixed, the used solvent is one of water, ethanol or isopropanol, the dispersant is polyethylene glycol, and the mass ratio of the dispersant to the inorganic particles is 1-10; the mass percentage of the inorganic particles in the inorganic particle slurry is 1-10%;
when the ablation-resistant resin, the catalyst and the solvent are prepared into an ablation-resistant resin solution, the catalyst is a weak base and comprises one or more of diluted ammonia water, sodium bicarbonate solution or potassium carbonate, and the mass ratio of the catalyst to the ablation-resistant resin is 1-10; the ablation-resistant resin solution comprises 20-60% of ablation-resistant resin by mass;
adding the inorganic particle slurry into the ablation-resistant resin solution, and stirring at room temperature for 1-10 hours to obtain an ablation-resistant matrix without sedimentation.
Furthermore, in the preparation method of the light dredging heat-proof and heat-insulating composite material, when the processes of heating, heat preservation, demoulding and drying are sequentially carried out, the heating temperature is 80-160 ℃, and the heat preservation time is 8-60 hours.
Compared with the prior art, the invention has the following beneficial effects:
(1) The light dredging heat-proof and heat-insulating composite material is designed by a high-porosity reinforcement structure and is prepared by adopting an ablation-resistant resin matrix, has excellent high-temperature resistance, and has long-term aerobic pneumatic thermal environmentThe medium line ablation rate is very low, the composite material has excellent heat insulation property and mechanical property, and the density of the composite material is between 0.3 and 0.8g/cm 3 The material can be used as a functional material of a large-area heat-proof and heat-insulating layer of an aerospace craft and a heat-proof and heat-insulating structural material with higher heat-proof and bearing requirements and more urgent weight reduction requirements.
(2) The light dredging heat-insulation-preventing composite material is a light hybrid fiber reinforcement with an alternate structure, and the upper/lower heat-insulation-preventing areas adopt a low-density needling structure of high-temperature-resistant inorganic fibers such as chopped quartz, high silica, alumina and the like, so that the density and the heat conductivity of the composite material are reduced, and the temperature resistance of a framework of the composite material is improved; the intermediate heat conducting area adopts continuous high heat conducting intermediate phase pitch carbon fiber braided fabric, so that the diffusivity of the intermediate heat layer is improved, the local high heat area on the surface layer can be favorably and rapidly transferred to the low heat area on the inner layer, the ablation degree and stagnation pressure of the upper/lower surface layers of the material are further reduced, the back temperature rise of the composite material is obviously reduced, and good heat-proof and heat-insulating comprehensive benefits are realized.
(3) The intermediate layer of the light dredging heat-insulation-preventing composite material reinforcement is prepared from high-heat-conduction intermediate-phase pitch carbon fibers, so that the mechanical property is excellent, particularly the modulus is very high, the temperature resistance and the high-temperature mechanical property of the material reinforcement framework are improved, the structural stability is still kept when the melting point of quartz fibers (about 1600 ℃) is exceeded, and the anti-scouring property of the material in the ablation process is favorably improved.
(4) The light dredging heat-proof and insulating composite material further improves the quality residual rate of a surface carbonization layer in the material ablation process and improves the ablation resistance by adding the high-temperature resistant inorganic particles into the ablation-resistant resin, more importantly, the components of the high-melting-point ceramic inorganic particles such as molybdenum silicide, silicon carbide and zirconium boride can be used at more than 1600 ℃, have very high radiation coefficient, particularly can keep high radiation coefficient in an aerobic environment, can effectively dissipate a large amount of surface heat energy by absorbing re-radiation in the ablation process, reduce the heat entering the material and improve the heat-proof efficiency.
(5) The light dredging heat-insulation-preventing composite material adopts a solution gel and vacuum impregnation resin transfer molding method, the forming process is simple to operate, the composite material with micro-nano apertures is obtained, the solid heat conduction and gas heat conduction of the composite material can be reduced, the matrix resin has higher radiance after ablation and cracking, and the radiation heat transfer of the composite material can be reduced, so the light dredging heat-insulation-preventing composite material has excellent heat-insulation performance.
Drawings
FIG. 1 is a schematic structural representation of a high porosity textile sandwich reinforcement obtained in examples 1 and 2 of the present invention;
figure 2 is a schematic representation of the high porosity textile sandwich reinforcement structure obtained in examples 3 and 4 of the present invention.
Detailed Description
The features and advantages of the present invention will become more apparent and apparent from the following detailed description of the invention.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. While the various aspects of the embodiments are presented in drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
The invention adopts novel dredging type thermal protection as passive thermal protection, which is different from the traditional thermal protection mechanism, adopts the physical characteristics of heat transfer, heat insulation and radiation heat dissipation of a heat-proof layer material to quickly transfer the heat in a high-heat flow area to a low-heat flow area, releases serious pneumatic heating in a radiation mode by means of a large amount of low-temperature area so as to reduce the temperature in the high-heat flow area, and reaches the level which can be borne by the existing high-temperature-resistant material, thereby realizing good thermal protection efficiency. According to the invention, the sparse heat protection layer is introduced into the porous organic resin-based ablation heat-proof material system, so that the high-efficiency heat management of quickly transferring a low-heat area in a local high-heat area is expected to be realized while the low density and excellent ablation and oxidation resistance of the heat-proof material are ensured, the ablation degree and stagnation pressure of the surface layer of the material are further reduced, and the long-term high-speed flight capability of the aerospace craft is obviously improved.
The invention provides a light dredging heat-insulation-preventing composite material, which comprises a high-porosity interlayer reinforcement and an ablation-resistant matrix, wherein the reinforcement comprises an interlayer structure consisting of an upper-layer high-temperature-resistant inorganic fiber needled fabric, a lower-layer high-temperature-resistant inorganic fiber needled fabric and a middle-layer high-heat-conductivity carbon fiber fabric, and the ablation-resistant matrix comprises ablation-resistant resin and inorganic particles; the total mass of the light dredging heat-insulation-preventing composite material is 100%, and the mass percentage of each component is as follows:
the upper layer and the lower layer of the reinforcement body are needling structure prefabricated bodies of high-temperature resistant inorganic fibers, and the high-temperature resistant fibers are quartz fibers, high silica fibers or alumina fibers;
the reinforcement middle layer is of a mesophase pitch carbon fiber fabric structure; and laying the reinforced layer between two high-temperature inorganic fiber fabric layers to obtain the high-porosity sandwich structure reinforcement.
The ablation-resistant matrix is linear phenolic aldehyde, high-carbon phenolic aldehyde or organic silicon resin;
the inorganic particles are at least one of molybdenum silicide, silicon carbide and zirconium boride.
The invention also provides a preparation method of the light dredging heat-insulation-preventing composite material, which comprises the following steps:
(1) Carding high silica fibers or quartz fibers or alumina fibers into a web tire, and performing lamination needling layer by layer to form an upper layer and a lower layer of the reinforcement;
(2) Weaving continuous high-thermal-conductivity carbon fibers into unidirectional, two-dimensional or three-dimensional multidirectional fabric to obtain a high-thermal-conductivity carbon fiber fabric layer, namely an intermediate layer of the reinforcement;
(3) Laying the high-thermal-conductivity carbon fiber fabric layer obtained in the step (2) on the reinforcement upper/lower layer structure obtained in the step (1), and laying the high-thermal-conductivity carbon fiber fabric layer between two high-temperature inorganic fiber fabric layers to obtain a high-porosity sandwich structure reinforcement with a high-thermal-conductivity carbon fiber intermediate layer;
(4) Mixing inorganic particles, a solvent and a dispersant, and ultrasonically dispersing for more than 2 hours to prepare slurry with the mass concentration of 1-10 wt%;
(5) Mixing and stirring ablation-resistant resin, a solvent and a catalyst uniformly to obtain an ablation-resistant resin solution with the mass concentration of 20-60%, then adding the slurry obtained in the step (4) into the ablation-resistant resin solution, and stirring at room temperature for 1-10 hours until no settlement occurs on the ablation-resistant matrix;
(6) Firstly, placing the high-porosity sandwich structure reinforcement obtained in the step (3) in a mould, then transferring and guiding the ablation-resistant matrix obtained in the step (5) into the mould through vacuum resin, sealing, heating to 80-160 ℃, carrying out heat preservation reaction for 8-60 hours, demoulding, and drying to obtain the light dredging heat-proof material, wherein the density of the light dredging heat-proof material is 0.3-0.8 g/cm 3 。
In the step (1), the density of the upper layer/the lower layer of the reinforcement body is 0.10-0.30 g/cm 3 The thickness is 1-20 mm.
In the step (2), the surface density of the reinforcement intermediate layer is 50-1000 g/m 2 The thickness is 0.5-10 mm.
In the step (2), the thermal conductivity of the continuous high-thermal-conductivity carbon fiber is not lower than 500W/(m.K).
In the step (4), the solvent is one of water, ethanol or isopropanol, the dispersant is polyethylene glycol, and the mass ratio of the dispersant to the inorganic particles is (10-100): 100.
In the step (5), the catalyst is weak base, including dilute ammonia, sodium bicarbonate solution, potassium carbonate and the like, and the mass ratio of the catalyst to the resin is (1-10): 100.
The composite material is prepared by selecting a high-porosity fabric interlayer prefabricated body as a reinforcement, adopting high-temperature-resistant inorganic fiber needled fabric as an upper and lower heat-insulation area, adopting high-heat-conductivity carbon fiber fabric as a middle heat-conduction layer, taking ablation-resistant resin and inorganic particles as a matrix system, and performing transfer molding by using vacuum impregnating resin. The density of the composite material is 0.3-0.8 g/cm 3 Linear ablation rate < 0.8 × 10 -3 mm/s, thermal conductivity of 0.04-0.1W/(m.K), excellent heat insulation and mechanical properties, and is suitable for large-area heat-insulation components of aerospace vehicles and heat-insulation systems with higher heat-insulation and bearing requirements.
The invention has high porosityThe upper/lower heat-insulation regions of the fiber reinforcement body adopt short-cut quartz fibers with low heat conductivity, short-cut high-silica fibers or short-cut alumina fibers with the density of 0.1-0.3 g/cm 3 The chopped fibers are carded into the web tire, and the web tire is needled layer by layer in a laminated manner, so that the consistency of the mechanical strength of the three-dimensional fabric reinforcement in the thickness direction is ensured.
The high-porosity fiber reinforcement intermediate layer heat conduction area adopts high-heat-conduction intermediate phase pitch carbon fibers with high heat conductivity, the heat conductivity is more than or equal to 500W/(mK), the intermediate layer is guaranteed to still keep high in-plane heat conductivity after being woven into unidirectional, planar or three-dimensional fabrics, and high heat energy of an ablation surface layer (namely an upper layer or a lower layer of a reinforcement) can be quickly transferred and diffused to a low-temperature area through the high-heat-conduction carbon fiber fabric intermediate layer; meanwhile, the high-thermal-conductivity carbon fiber intermediate layer has excellent mechanical properties, particularly the tensile modulus of the fiber is more than or equal to 800GPa, so that the temperature resistance and the high-temperature mechanical properties of the material reinforcement framework can be improved, the structural stability is still kept when the temperature exceeds the melting point (about 1600 ℃) of quartz fiber, and the anti-scouring performance of the material in the ablation process is favorably improved.
The inorganic particles are one or the combination of more than one of molybdenum silicide, silicon carbide or zirconium boride. In order to further improve the radiation heat dissipation capacity of the surface of the material and further improve the heat insulation prevention efficiency of the material, the high-temperature-resistant, oxidation-resistant and high-emissivity ceramic inorganic particles such as molybdenum silicide, silicon carbide, zirconium boride and the like are added into the ablation-resistant matrix, so that the oxidation resistance of the material is favorably improved, and the ablation rate is reduced.
The ablation-resistant resin forms a resin matrix in the composite material finally by a sol-gel method, so that the uniform dispersion of high-temperature-resistant inorganic particles in the porous organic resin matrix is realized, a proper catalyst is selected to promote a crosslinking reaction, a cured substance is formed, a solvent escapes from the composite material by drying at normal pressure in the later stage, micron pores are formed, the thermal conductivity of the material can be reduced, and the composite material has excellent heat-insulating property.
Example 1
Carding the quartz fiber into a web blank, needling the quartz fiber into a quartz fiber fabric with the thickness of about 10mm in a layer-by-layer laminated manner,namely, the upper layer and the lower layer, (the density is 0.15 g/cm) 3 ) (ii) a Weaving continuous high-heat-conductivity carbon fibers (the brand: XN-90, the heat conductivity is 500W/mK) into two-dimensional plain cloth (the surface density is 800 g/m) 2 Single layer thickness 0.6 mm), as shown in fig. 1, two layers of carbon fiber plain cloth are overlaid on the surface of the quartz fiber fabric to form a reinforcement middle layer with the thickness of about 1.2 mm; and then clamping the high-thermal-conductivity carbon fiber intermediate layer by using another layer of quartz fiber fabric to form a reinforcement with the thickness of about 21mm, namely obtaining the reinforcement with the high-porosity fiber sandwich structure, and then filling the reinforcement into a steel mould.
Molybdenum silicide according to the mass ratio of raw materials: ethanol: mixing polyethylene glycol = 5; according to the mass ratio of the raw materials, the linear phenolic resin: mixing and stirring ethanol and dilute ammonia water = 50; then adding the slurry into an ablation-resistant resin solution, and stirring for 2 hours at room temperature until no sedimentation occurs to the ablation-resistant matrix; transferring and guiding the ablation-resistant matrix into a mold through vacuum impregnating resin, sealing, heating to 100 ℃, carrying out heat preservation reaction for 24 hours, demolding, and drying to obtain the light dredging heat-proof material.
The average density of the material was 0.35g/cm 3 The average thermal conductivity is 0.05W/(m.K), the thickness of the middle layer is 1mm, and the thicknesses of the upper and lower heat-proof layers are about 9.5mm respectively; the compressive strength in the thickness direction was 8MPa (10% strain), and the compressive strength in the plane direction was 12MPa;1.0MW/m 2 The linear ablation amount of oxyacetylene ablation is 0.15mm per 1000s, and the maximum temperature rise of the back surface is 180 ℃.
Example 2
Carding the chopped quartz fiber into a web blank, and needling the web blank layer by layer to form a quartz fabric with the thickness of about 10mm, namely an upper layer and a lower layer (the density is 0.15 g/cm) 3 ) (ii) a Weaving continuous high-heat-conductivity carbon fibers (the brand: TYG-1, the heat conductivity is 600W/mK) into two-dimensional plain cloth (the surface density is 600 g/m) 2 The single layer thickness is 0.22 mm), five layers of carbon fiber plain cloth are stacked to form a reinforcement middle layer with the thickness of about 1.1 mm; as shown in fig. 1, an upper layer and a lower layer of quartz fiber fabrics are clamped between high-thermal-conductivity carbon fiber intermediate layers to form a reinforcement with the thickness of about 21mm, and the reinforcement of the high-void-ratio fiber sandwich structure is obtainedThe bodies were then loaded into steel molds.
Molybdenum silicide according to the mass ratio of raw materials: ethanol: mixing polyethylene glycol = 5; the phenolic resin comprises the following raw materials in percentage by mass: mixing and stirring ethanol and dilute ammonia water = 50; then adding the slurry into an ablation-resistant resin solution, and stirring for 2 hours at room temperature until no sedimentation occurs to the ablation-resistant matrix; transferring the ablation-resistant matrix into a mold through vacuum impregnating resin, sealing, heating to 100 ℃, carrying out heat preservation reaction for 24 hours, demolding, and drying to obtain the light dredging heat-proof material.
The average density of the material was 0.40g/cm 3 The average thermal conductivity is 0.08W/(m.K), the thickness of the middle layer is 1mm, and the thicknesses of the upper and lower heat-proof layers are about 9.5mm respectively; the compressive strength in the thickness direction was 8MPa (10% strain), and the compressive strength in the plane direction was 11MPa;1.0MW/m 2 The linear ablation amount of oxyacetylene ablation per 1000s was 0.14mm, and the maximum temperature rise of the back surface was 170 ℃.
Example 3
Carding high silica fiber into web, and needling layer by layer to form high silica fiber fabric (density 0.20 g/cm) with thickness of about 10mm 3 ) (ii) a Continuous high-heat-conductivity carbon fibers (brand: XN-90, heat conductivity 500W/mK) are woven into two-dimensional plain cloth (surface density 800 g/m) 2 The thickness of a single layer is 0.6 mm), two layers of carbon fiber plain cloth are overlaid to form a reinforcement middle layer with the thickness of about 1.2 mm; as shown in fig. 2, a high thermal conductivity carbon fiber intermediate layer is sandwiched between each two layers of three layers of high silica fiber fabrics to form a reinforcement with a thickness of about 32mm separating the two intermediate layers, so as to obtain a high-porosity sandwich structure reinforcement, and then the reinforcement is placed in a steel mold.
Molybdenum silicide according to the mass ratio of raw materials: water: mixing polyethylene glycol =10 and 5; the high-carbon phenolic resin comprises the following raw materials in percentage by mass: the isopropanol and sodium bicarbonate solution = 45; then adding the slurry into an ablation-resistant resin solution, and stirring for 10 hours at room temperature until no settlement occurs on the ablation-resistant matrix; transferring the ablation-resistant matrix into a mold through vacuum impregnating resin, sealing, heating to 120 ℃, carrying out heat preservation reaction for 12 hours, demolding, and drying to obtain the light dredging heat-proof material.
The average density of the material was 0.60g/cm 3 The average thermal conductivity is 0.06W/(m.K), the thicknesses of the middle layers are respectively 1mm, and the thicknesses of the three heat-proof and insulating layers are respectively about 9.5mm; a compressive strength in the thickness direction of 11MPa (10% strain) and a compressive strength in the plane direction of 16MPa;1.0MW/m 2 The linear ablation amount of the oxyacetylene ablation per 1000s is 0.13mm, and the maximum temperature rise of the back surface is 150 ℃.
Example 4
Carding high silica fiber into web, and needling layer by layer to form high silica fiber fabric (density 0.20 g/cm) with thickness of about 10mm 3 ) (ii) a Weaving continuous high-heat-conductivity carbon fibers (the brand: TYG-1, the heat conductivity is 600W/mK) into two-dimensional plain cloth (the surface density is 600 g/m) 2 The thickness of a single layer is 0.22 mm), five layers of carbon fiber plain cloth are overlaid to form a reinforcement middle layer with the thickness of about 1.1 mm; as shown in fig. 2, a high thermal conductivity carbon fiber intermediate layer is sandwiched between each two layers of three layers of high silica fiber fabrics to form a reinforcement with a thickness of about 32mm separating the two intermediate layers, so as to obtain a high-porosity sandwich structure reinforcement, and then the reinforcement is placed in a steel mold.
Molybdenum silicide according to the mass ratio of raw materials: water: mixing polyethylene glycol =10 and 5 in proportion, and ultrasonically dispersing for 10 hours to prepare slurry with the mass concentration of 10 wt%; the high-carbon phenolic resin comprises the following raw materials in percentage by mass: the isopropanol and sodium bicarbonate solution = 45; then adding the slurry into an ablation-resistant resin solution, and stirring for 10 hours at room temperature until no settlement occurs on the ablation-resistant matrix; transferring the ablation-resistant matrix into a mold through vacuum impregnating resin, sealing, heating to 120 ℃, carrying out heat preservation reaction for 12 hours, demolding, and drying to obtain the light dredging heat-proof material.
The average density of the material was 0.63g/cm 3 The average thermal conductivity is 0.06W/(m.K), the thicknesses of the two intermediate layers are respectively 1mm, and the thicknesses of the three-proof heat-insulating layers are respectively about 95mm; a compressive strength in the thickness direction of 10MPa (10% strain) and a compressive strength in the plane direction of 17MPa;1.0MW/m 2 The linear ablation amount of oxyacetylene ablation is 0.13mm per 1000s, and the maximum temperature rise of the back surface is 120 ℃.
Comparative example 1
Carding the quartz fiber into a web, and needling the web layer by layer to form a quartz fiber fabric (the density is 0.15 g/cm) with the thickness of about 10mm 3 ) (ii) a The reinforcement is formed to a thickness of about 20mm and then loaded into a steel mold.
Molybdenum silicide according to the mass ratio of raw materials: ethanol: mixing polyethylene glycol = 5; according to the mass ratio of the raw materials, the linear phenolic resin: ethanol and dilute ammonia = 50; then adding the slurry into an ablation-resistant resin solution, and stirring for 2 hours at room temperature until no settlement occurs on the ablation-resistant matrix; transferring the ablation-resistant matrix into a mold through vacuum impregnating resin, sealing, heating to 100 ℃, carrying out heat preservation reaction for 24 hours, demolding, and drying to obtain the light dredging heat-proof material.
The average density of the material was 0.32g/cm 3 The average thermal conductivity was 0.05W/(m.K), the compressive strength in the thickness direction was 5MPa (10% strain), and the compressive strength in the plane direction was 8MPa;1.0MW/m 2 The linear ablation amount of oxyacetylene ablation per 1000s was 0.25mm, and the maximum temperature rise of the back surface was 242 ℃.
Comparative example 2
Carding high silica fiber into web, and needling layer by layer to form high silica fiber fabric (density 0.20 g/cm) with thickness of about 10mm 3 ) Three layers of high silica fiber fabric are superposed to form a reinforcing body with the thickness of about 30mm, and then the reinforcing body is arranged in a steel mould.
Molybdenum silicide according to the mass ratio of raw materials: water: mixing polyethylene glycol =10 and 5; the material mass ratio is high than the high carbon phenolic resin: the isopropanol and sodium bicarbonate solution = 45; then adding the slurry into an ablation-resistant resin solution, and stirring for 10 hours at room temperature until no settlement occurs on the ablation-resistant matrix; transferring and guiding the ablation-resistant matrix into a mold through vacuum impregnating resin, sealing, heating to 120 ℃, carrying out heat preservation reaction for 12 hours, demolding, and drying to obtain the light dredging heat-proof material.
The average density of the material was 0.56g/cm 3 The average thermal conductivity was 0.056W/(m.K), the compressive strength in the thickness direction was 7MPa (10% strain), and the compressive strength in the plane direction was 10MPa;1.0MW/m 2 The linear ablation amount of oxyacetylene ablation per 1000s was 0.21mm, and the maximum temperature rise of the back surface was 204 ℃.
The above comparative example 1 was identical to example 1 except that the high thermal conductive carbon fiber intermediate layer was not added, and the comparative example 2 was identical to example 3 except that the high thermal conductive carbon fiber intermediate layer was not added, and it can be seen from the test results of comparative example 1 and example 1, and comparative example 2 and example 3 that the linear ablation amount and the back peak temperature of the composite material to which the high thermal conductive carbon fiber intermediate layer was added were significantly reduced.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to limit the invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Those skilled in the art will appreciate that those matters not described in detail in the present specification are well known in the art.
Claims (10)
1. A light dredging heat-proof composite material is characterized by comprising a reinforcement body and an ablation-resistant matrix;
the reinforcement is of a sandwich structure and comprises a high-temperature-resistant inorganic fiber fabric layer and a high-heat-conductivity carbon fiber fabric layer, wherein each high-heat-conductivity carbon fiber fabric layer is sandwiched between two high-temperature-resistant inorganic fiber fabric layers;
the ablation-resistant matrix comprises an ablation-resistant resin and inorganic particles;
the total mass of the light dredging heat-proof and heat-insulating composite material is 100%, and the weight percentage content of each component is as follows:
40-50% of high-temperature resistant inorganic fiber fabric;
10-20% of high-thermal-conductivity carbon fiber fabric;
30-50% of ablation-resistant resin;
1 to 5 percent of inorganic particles;
the high-temperature resistant inorganic fiber in the high-temperature resistant inorganic fiber fabric layer is one or the combination of more than one of quartz fiber, high silica fiber or alumina fiber; and the high-heat-conductivity carbon fibers in the high-heat-conductivity carbon fiber fabric layer are mesophase pitch carbon fibers.
2. The composite material of claim 1, wherein the reinforcement comprises 1-3 layers of high thermal conductivity carbon fiber fabric.
3. The light dredging, heat preventing and insulating composite material as claimed in claim 1, wherein the high temperature resistant inorganic fiber fabric layer is a needle felt of high temperature resistant inorganic fibers;
the ablation-resistant substrate is a porous material with micron-sized pores;
the high-thermal-conductivity carbon fiber fabric layer is a unidirectional fabric, a two-dimensional multidirectional fabric or a three-dimensional multidirectional fabric;
the ablation-resistant resin is one or more of linear phenolic resin, high-carbon phenolic resin or organic silicon resin;
the inorganic particles are one or the combination of more than one of molybdenum silicide, silicon carbide or zirconium boride.
4. The light dredging heat-proof insulation composite material as claimed in claim 1, wherein the density of the high temperature resistant inorganic fiber fabric layer in the reinforcement is 0.10-0.30 g/cm 3 The thickness is 1-20 mm.
5. According to the claimThe light dredging heat-proof composite material obtained in claim 1 is characterized in that the surface density of the high-thermal-conductivity carbon fiber fabric layer in the reinforcement is 50-1000 g/m 2 The thickness is 0.5-10 mm;
the average density of the light dredging heat-proof composite material is 0.3-0.8 g/cm 3 。
6. The light dredging, heat preventing and insulating composite material as claimed in claim 1, wherein the thermal conductivity of the high thermal conductive carbon fibers in the high thermal conductive carbon fiber fabric layer is not lower than 500W/(m-K).
7. A preparation method of a light dredging heat-proof and heat-insulating composite material is characterized by comprising the following steps:
carding the high-temperature-resistant inorganic fibers into a net tire, and needling a plurality of layers of net tires layer by layer in a laminated manner to form a high-temperature-resistant inorganic fiber fabric layer; the high-temperature resistant inorganic fiber is one or more of quartz fiber, high silica fiber or alumina fiber;
weaving continuous high-thermal-conductivity carbon fibers into a high-thermal-conductivity carbon fiber fabric to obtain a high-thermal-conductivity carbon fiber fabric layer; the high-thermal-conductivity carbon fibers are mesophase pitch carbon fibers;
laying a high-thermal-conductivity carbon fiber fabric layer between two high-temperature inorganic fiber fabric layers to obtain a reinforcement of a sandwich structure;
mixing inorganic particles, a solvent and a dispersing agent, and performing ultrasonic dispersion to obtain inorganic particle slurry;
preparing ablation-resistant resin solution from ablation-resistant resin, a catalyst and a solvent, adding inorganic particle slurry into the ablation-resistant resin solution, and stirring to obtain an ablation-resistant matrix;
placing the reinforcement in a mold, introducing the ablation-resistant matrix into the mold by adopting a vacuum resin transfer process, and sequentially performing heating, heat preservation, demolding and drying to obtain the material with the density of 0.3-0.8 g/cm 3 The light dredging heat-insulating composite material.
8. The method for preparing the light dredging heat-proof insulation composite material according to claim 7, wherein the ablation-resistant resin is one or more of a linear phenolic resin, a high-carbon phenolic resin or a silicone resin;
the inorganic particles are one or the combination of more than one of molybdenum silicide, silicon carbide or zirconium boride.
9. The preparation method of the light dredging heat-proof insulation composite material according to claim 7, characterized in that when inorganic particles, a solvent and a dispersant are mixed, the solvent is one of water, ethanol or isopropanol, the dispersant is polyethylene glycol, and the mass ratio of the dispersant to the inorganic particles is 1-10; the mass percentage of the inorganic particles in the inorganic particle slurry is 1-10%;
when the ablation-resistant resin, the catalyst and the solvent are prepared into an ablation-resistant resin solution, the catalyst is a weak base and comprises one or more of diluted ammonia water, sodium bicarbonate solution or potassium carbonate, and the mass ratio of the catalyst to the ablation-resistant resin is 1-10; the ablation-resistant resin solution comprises 20-60% of ablation-resistant resin by mass;
adding the inorganic particle slurry into the ablation-resistant resin solution, and stirring at room temperature for 1-10 hours to obtain an ablation-resistant matrix without sedimentation.
10. The preparation method of the light dredging heat-proof insulation composite material according to claim 7, wherein the heating temperature is 80-160 ℃ and the heat preservation time is 8-60 hours when the processes of heating, heat preservation, demoulding and drying are sequentially carried out.
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| WO2024098254A1 (en) * | 2022-11-08 | 2024-05-16 | 宁德时代新能源科技股份有限公司 | Heat-resistant protective component and battery |
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| WO2024098254A1 (en) * | 2022-11-08 | 2024-05-16 | 宁德时代新能源科技股份有限公司 | Heat-resistant protective component and battery |
| CN115636683A (en) * | 2022-12-08 | 2023-01-24 | 北京玻钢院复合材料有限公司 | Fiber mixed fabric reinforced quartz-based composite material and preparation method thereof |
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| CN115179609B (en) | 2024-03-15 |
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